CN105670207A - Lightweight antibacterial electronic cigarette shell and preparation method thereof - Google Patents

Lightweight antibacterial electronic cigarette shell and preparation method thereof Download PDF

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Publication number
CN105670207A
CN105670207A CN201610043719.2A CN201610043719A CN105670207A CN 105670207 A CN105670207 A CN 105670207A CN 201610043719 A CN201610043719 A CN 201610043719A CN 105670207 A CN105670207 A CN 105670207A
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cigarette shell
electronics cigarette
antibacterial
lightweight
preparation
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CN105670207B (en
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李典
田兆福
陆漓
梁俊
黄忠辉
王萍娟
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China Tobacco Guangxi Industrial Co Ltd
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China Tobacco Guangxi Industrial Co Ltd
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/107—Nitroso compounds
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    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
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    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2205/00—Polymer mixtures characterised by other features
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  • Polymers & Plastics (AREA)
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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention discloses a lightweight antibacterial electronic cigarette shell and a preparation method thereof.The preparation method includes: in the process of polymer mixing, adding nucleating agent, foaming agent, foaming auxiliary and toughening agent; foaming and forming in a tubular die to obtain a foamed polymer pipe, and cutting the foamed polymer pipe to obtain the electronic cigarette shell of certain length.By using the electronic cigarette shell prepared by the method, weight of an electronic cigarette is effectively reduced; nano ZnO used in the foaming auxiliary is of a hollow porous structure, and more active oxygen and active zinc ions can be generated to realize antibacterial effect.The preparation method is easy in raw material getting and simple in synthesis step, and the lightweight antibacterial electronic cigarette shell can be obtained.

Description

The electronics cigarette shell that a kind of lightweight is antibacterial and its preparation method
Technical field
The invention belongs to technical field of composite materials, the electronics cigarette shell antibacterial in particular to a kind of lightweight and its preparation method.
Background technology
Electronics cigarette is a kind of electronic product imitating traditional cigarette, has the outward appearance the same with cigarette, smog, taste and sense organ. But inside electronics cigarette, have the existence of battery and cigarette bullet, and wrap up as supporting outer by hard material (such as metal, rigid plastics etc.), therefore much bigger compared with its weight traditional cigarette, even some is beyond more than 10 times, this by impression human consumer to a great extent to the sensory evaluation of electronics cigarette. So the weight how reducing electronics cigarette is also a difficult problem in electronics cigarette technology.
In order to reduce the weight of plastic component under same volume, it is possible to adopt the method for foaming, plastic component adds certain nontoxic gas, reduce the density of plastic component, finally reach the weight reducing plastic component. Preparing in foamed polymer material, it is possible to adopt microporous foam and constructional foaming, selecting different foaming methods according to the character of different polymkeric substance, generally the apparent density of polymkeric substance can be dropped to original 50%～80%. And, the foamed polymer material obtained due to its have dense skin, inner be microvoid structure, funny high than unfoamed material of the same race of the intensity of its unit mass and shock resistance, thus subtract heavy while also can improve the mechanical property of material to a certain extent.
In addition, polymer foaming material blended in the middle of, it is necessary to add certain frothing aid (helping nucleator) ZnO and TiO2, the oxide compound of these Nano grades has certain antibacterial ability, and this had been reported in a large number. So be dispersed in the help nucleation foaming of fluoropolymer resin at nano-ZnO while, antibacterial effect also can be played in the polymer materials of final molding. And the ZnO nanoparticle reported in the past is all exposed (after high-temperature calcination, stablizer all disappears) in the rear surface prepared, therefore dispersion in water or in the middle of polymkeric substance is very poor, it is necessary in further modification. If modifying the excessive ability decline that ZnO nanoparticle surface may be caused to receive light, can not well give play to antibacterial mechanism. Nearest proposition hydrothermal method prepares ZnO by calcining directly dehydration formation ZnO nanoparticle under high-temperature water heat effect, so just can not preserve the component of destabilizing agent preferably.On the other hand, also have report the nanoparticle with point level structure can better absorb light the ability that transforms, the ZnO therefore preparing structure special can strengthen its antibacterial effect.
Consider that electronics cigarette needs repeatedly to use, antibacterial performance requriements is also higher. So adopting to have the nano-ZnO of special construction can not only effectively reduce the weight of electronics cigarette as foamable polymer resin that the mode injection moulding of frothing aid obtains, moreover it is possible to reach antibacterial effect, it is the antibacterial electronics cigarette shell preparation method of a kind of lightweight.
Summary of the invention
It is an object of the invention to provide the sterilized electronic cigarette shell preparation method of a kind of lightweight. The sterilized electronic cigarette shell of described lightweight is specially a kind of foamable polymer tubing being mixed with hollow porous nanometer ZnO powder. By taking the cross-linked polymer containing a large amount of carboxyl such as PAA as template, Zn in complexing2+, when high score high pressure, and the OH that the hydrolysis of the amine substance such as urea generates-Reaction, in-situ preparation Zn (OH) on PAA2, and continue dehydration under this condition and define the ZnO of crystallization, form shell on PAA surface; In the process that ZnO is formed, under highly basic high temperature action, inner PAA occurs solution crosslinked, forms PAA chain, runs out of, and complexing is on the surface of ZnO, become the stablizer of ZnO, and vacated by the shell of centre, and produce cinclides from the shell of ZnO. Such hollow porous ZnO is as the frothing aid of expanded plastic and antiseptic-germicide, apparent density not only gently contributes to reducing the weight of plastics, moreover it is possible to give big specific surface area for the absorption of light and in the inner look refraction of particle to produce active oxygen or active zinc ion carrys out the generation of anti-bacteria.
On the other hand, in order to ensure not affect original performance of original polymer shell, as having good shock resistance, thermotolerance is strong, erosion resistance good, insulation, heat-insulating property etc., gas release used in the present invention is moderate, micro-bubble of enough amounts can be produced in the polymeric material, while its original performance can not only be ensured, strengthen its some performance to a certain extent. But gas release is unsuitable excessive, excessive gas release can make polymkeric substance become crisp, frangible so that polymer performance declines greatly. Finally the foamable polymer tubing obtained can be cut into electronics cigarette shell according to the specification of electronics cigarette.
It is an object of the invention to provide the sterilized electronic cigarette shell of a kind of lightweight and its preparation method
The electronics cigarette shell preparation method that a kind of lightweight of the present invention is antibacterial, comprises the steps:
Step one, the polyacrylic acid PAA crosslinked by 0.1～5 weight part or crosslinked polymethyl acrylic acid PMAA is dispersed in the middle of the deionized water of 25～500 weight parts, adding soluble zinc salt 0.1～2.5 weight part and aminated compounds 0.4～8 weight part, stirring and dissolving, obtains reaction system; Reaction system is transferred in stainless steel autoclave, airtight good after transfer in the middle of baking oven, react 12～36 hours at 120～200 DEG C; Reactor being down to room temperature, under the rotating speed of 5000～12000rpm centrifugal 2～10 minutes, isolate hollow porous ZnO, with deionized water wash 3～5 times, at 40～60 DEG C, dry 24h, obtains hollow porous nanometer ZnO powder;
Step 2, the whipping agent of the polymer masterbatch of 1～5 weight part porous hollow nanometer ZnO powder, 80～100 weight parts, 5～10 part by weight modified auxiliary agents, 1～3 weight parts of calcium carbonate and 1～4 weight part is added kneader heating kneading 1～5h, then joins in mixing roll;Mixing roll is injected in the middle of tubular die by high-voltage high-speed, is 2～7MPa in mold pressing, when temperature is 50～80 DEG C, adopts low pressure foaming, polymer melt is carried out foaming; The cooling of shaping complete shell is deviate from from mould, obtains the aseptic tubing of foaming after dry, to tubing cutting, obtain the electronics cigarette shell that lightweight is antibacterial.
Further improvement, described crosslinked PAA or crosslinked PMAA is prepared by distillation precipitation polymerization; The linking agent used is bi-vinyl bisacrylamide class linking agent, bi-vinyl di-esters linking agent or double-vinyl benzene class linking agent.
Further improvement, the particle diameter of described crosslinked polyacrylic acid PAA or crosslinked polymethyl acrylic acid PMAA is 50～500nm, and degree of crosslinking is 10%～50%.
Further improvement, in described step one, it may also be useful to crosslinked PAA.
Further improvement, in described step one, soluble zinc salt is ZnCl2、Zn(NO3)2、ZnSO4Or zinc acetate.
Further improvement, in described step one, aminated compounds is urea, six methyne four ammoniums, hydrazine hydrate, thanomin, diethanolamine and trimeric cyanamide.
Further improvement, in described step 2, polymer masterbatch is PC resin, ABS resin or both mixtures.
Further improvement, in described step 2, described modified additive is made up of the frothing aid of the antioxidant of 5～20 weight parts, 0～30 weight part and the toughner of 20～80 weight parts, and wherein toughner is one or several the mixture in SBS, SEBS and EVA; Frothing aid is TiO2Or TiO2With the mixture of ZnO; Antioxidant is quinoline derivatives, phosphite analog derivative.
Further improvement, whipping agent described in described step 2 is azo-compound, nitroso compound or the sodium carbonate salt master batch ball through polymer support Resin adhesive encapsulated.
The relative density of the polymer pipe that the aseptic foamable polymer tubing of a kind of lightweight that the present invention obtains is more original reduces 10%～60%.
The present invention prepares hollow porous ZnO nanoparticle by the mode of hydro-thermal, it is possible to saves the process that high sublevel burns, decreases the sintering between particle; Core PAA separates and crosslinked not only defines hollow structure in original position to ZnO particle, and its PAA chain loose out can also become the stablizer of ZnO so that its dispersion in the polymer improves further, modifies without coupling agent again.
The raw material of the aseptic foamable polymer tubing that the present invention prepares a kind of lightweight is easy to get, and synthesis step is simple, and the electronics cigarette shell preparation antibacterial for a kind of lightweight will have market application foreground widely.
Compared with prior art, the advantage of the present invention is:
1. the hollow porous ZnO made in the present invention is as the frothing aid of expanded plastic and antiseptic-germicide, apparent density not only gently contributes to reducing the weight of plastics, moreover it is possible to give big specific surface area for the absorption of light and in the inner look refraction of particle to produce active oxygen or active zinc ion carrys out the generation of anti-bacteria.
2. in order to ensure not affect original performance of original polymer shell, as having good shock resistance, thermotolerance is strong, erosion resistance good, insulation, heat-insulating property etc., gas release used in the present invention is moderate, micro-bubble of enough amounts can be produced in the polymeric material, while its original performance can not only be ensured, strengthen its some performance to a certain extent. But gas release is unsuitable excessive, excessive gas release can make polymkeric substance become crisp, frangible so that polymer performance declines greatly.Finally the foamable polymer tubing obtained can be cut into electronics cigarette shell according to the specification of electronics cigarette.
3. the relative density of the polymer pipe that the aseptic foamable polymer tubing of a kind of lightweight that the present invention obtains is more original reduces 10%～60%. The present invention prepares hollow porous ZnO nanoparticle by the mode of hydro-thermal, it is possible to saves the process that high sublevel burns, decreases the sintering between particle; Core PAA separates and crosslinked not only defines hollow structure in original position to ZnO particle, and its PAA chain loose out can also become the stablizer of ZnO so that its dispersion in the polymer improves further, modifies without coupling agent again.
4. the raw material of the aseptic foamable polymer tubing that the present invention prepares a kind of lightweight is easy to get, and synthesis step is simple, and the electronics cigarette shell preparation antibacterial for a kind of lightweight will have market application foreground widely.
Accompanying drawing explanation
Fig. 1 is the preparation process schematic diagram of hollow porous ZnO nanoparticle;
Fig. 2 is the scanning electron microscope diagram of hollow porous ZnO nanoparticle in embodiment 1-7;
Fig. 3 is the transmission electron microscope figure of single hollow porous ZnO nanoparticle in embodiment 1-7.
Embodiment
In order to make those skilled in the art understand the technical scheme of the present invention better, and make the above-mentioned feature of the present invention, object and advantage more clear understandable, now the present invention is further explained explanation in conjunction with the embodiments, it should be noted that, the all embodiments listed at this are only explanation property, and do not mean that and the scope of the invention limited. Material used in embodiment, instrument etc. are all commercially available prod. Whipping agent used in embodiment is azo-compound, nitroso compound or the sodium carbonate salt master batch ball through polymer support Resin adhesive encapsulated. Crosslinked PAA or crosslinked PMAA is prepared by distillation precipitation polymerization; The linking agent used is bi-vinyl bisacrylamide class linking agent, bi-vinyl di-esters linking agent or double-vinyl benzene class linking agent; The antioxidant that the antioxidant used is commercialization, its trade name is respectively antioxidant 1010, antioxidant 1076 and antioxidant 168, and its effective constituent is quinoline derivatives or phosphite analog derivative.
Fig. 1 is the preparation process schematic diagram of hollow porous ZnO nanoparticle: in the deionized water system 1, coexisted containing the polyacrylic acid microballoon of a large amount of carboxyl, zinc salt, urea at rich surface, first it is that the amine substance hydrolysis generation alkali environment such as urea make zinc salt formation zinc hydroxide under high temperature action, and become fine particle to be attached to and form shell on the polyacrylic acid microballoon of the negative charge having carboxyl, be i.e. the nucleocapsid structure microballoon of polyacrylic acid zinc hydroxide; 2, along with reaction continues, the hydroxide zinc layers on surface becomes thick gradually, and the polyacrylic acid microballoon of inside can be hydrolyzed by high temperature strong alkali environment slowly that produce, namely defines shell and becomes the nucleocapsid structure microballoon that big heart becomes the polyacrylic acid zinc hydroxide fallen apart; 3, the crystallization of dewatering under high temperature hydrothermal condition of the hydroxide zinc layers on last surface generates zinc oxide, and the polyacrylic acid microballoon of centre is completely degraded and is dissolved in water and leaves cavity, finally defines zinc oxide hollow particle.
Embodiment 1:
As template taking the polyacrylic acid PAA (as 150nm, degree of crosslinking is 25% to particle diameter) that 0.5g is crosslinked, it is dispersed in the middle of 200mL deionized water, finally adds ZnCl20.5g and urea 1.0g, and evenly stir and make it be dissolved completely in water.Whole system is transferred in the tetrafluoroethylene liner (volume is 300mL) of stainless steel autoclave, airtight good after transfer in the middle of baking oven, be heated to 120 DEG C and keep 36 hours. After reaction terminates, reactor is dropped to room temperature, by the mode of centrifugal (the centrifugal 10min of 5000rpm), the hollow porous ZnO obtained is separated, with deionized water wash 5 times, by vacuum drying method drying one day at 60 DEG C, both obtained hollow porous nanometer ZnO powder.
By the TiO of the antioxidant 1010 of 5 weight parts, 10 weight parts2The SBS mixing of frothing aid and 30 weight parts, makes modified additive. Then the whipping agent of the ABS masterbatch of 86 parts, 7 parts of modified additives, 3 parts of porous hollow nanometer ZnO powder, 3 parts of calcium carbonate and 1 part is added after kneader heating mediates 5h, join in mixing roll. Being injected in the middle of tubular die by high-voltage high-speed in mixing roll, adopt low pressure foaming, be 7MPa in mold pressing, temperature is, at 80 DEG C, polymer melt is carried out foaming. Finally the cooling of shaping complete shell is deviate from from mould, after dry, obtain the aseptic tubing of foaming. After tubing is carried out cutting, the electronics cigarette shell that a kind of lightweight is antibacterial can be obtained. Prepare whipping agent addition 1%, nano-ZnO addition be 3% the sterilized electronic cigarette shell of lightweight, the tubing (not adding whipping agent) that its weight is more original have dropped 22%. Fig. 2 is the scanning electron microscope diagram of hollow porous ZnO nanoparticle; Fig. 3 is the transmission electron microscope figure of single hollow porous ZnO nanoparticle.
Embodiment 2:
Hollow porous nanometer ZnO powder preparation method is see embodiment 1.
Described modified additive is by the TiO of antioxidant 1076,15 weight part of 20 weight parts2, the ZnO of 15 weight parts and 20 weight parts SEBS mixing, make modified additive. The whipping agent of the ABS masterbatch of 85 parts, 7 parts of modified additives, 3 parts of porous hollow nanometer ZnO powder, 3 parts of calcium carbonate and 2 parts is added after kneader heating mediates 1h, join in mixing roll. Being injected in the middle of tubular die by high-voltage high-speed in mixing roll, adopt low pressure foaming, be 2MPa in mold pressing, temperature is, at 50 DEG C, polymer melt is carried out foaming. Finally the cooling of shaping complete shell is deviate from from mould, after dry, obtain the aseptic tubing of foaming. After tubing is carried out cutting, the electronics cigarette shell that a kind of lightweight is antibacterial can be obtained. Prepare whipping agent addition 2%, nano-ZnO addition be 3% the sterilized electronic cigarette shell of lightweight, the tubing (not adding whipping agent) that its weight is more original have dropped 37%.
Embodiment 3:
Hollow porous nanometer ZnO powder preparation method is see embodiment 1.
By the TiO of antioxidant 1076,20 weight part of 5 weight parts2Mix with the increasing EVA of 80 weight parts, make modified additive. The whipping agent of the ABS masterbatch of 84 parts, 7 parts of modified additives, 3 parts of porous hollow nanometer ZnO powder, 3 parts of calcium carbonate and 3 parts is added after kneader heating mediates 3h, join in mixing roll. Being injected in the middle of tubular die by high-voltage high-speed in mixing roll, adopt low pressure foaming, be 5MPa in mold pressing, temperature is, at 70 DEG C, polymer melt is carried out foaming. Finally the cooling of shaping complete shell is deviate from from mould, after dry, obtain the aseptic tubing of foaming. After tubing is carried out cutting, the electronics cigarette shell that a kind of lightweight is antibacterial can be obtained. Prepare whipping agent addition 3%, nano-ZnO addition be 3% the sterilized electronic cigarette shell of lightweight, the tubing (not adding whipping agent) that its weight is more original have dropped 53%.
Embodiment 4:
Hollow porous nanometer ZnO powder preparation method is see embodiment 1.
Described modified additive is by the TiO of antioxidant 1076,15 weight part of 10 weight parts2Mix with the SEBS of the SBS of 20 weight parts, 20 weight parts, make modified additive. The whipping agent of the ABS masterbatch of 87 parts, 7 parts of modified additives, 1 part of porous hollow nanometer ZnO powder, 3 parts of calcium carbonate and 2 parts is added after kneader heating mediates 1h, join in mixing roll. Being injected in the middle of tubular die by high-voltage high-speed in mixing roll, adopt low pressure foaming, be 7MPa in mold pressing, temperature is, at 80 DEG C, polymer melt is carried out foaming. Finally the cooling of shaping complete shell is deviate from from mould, after dry, obtain the aseptic tubing of foaming. After tubing is carried out cutting, the electronics cigarette shell that a kind of lightweight is antibacterial can be obtained. Prepare whipping agent addition 2%, nano-ZnO addition be 1% the sterilized electronic cigarette shell of lightweight, the tubing (not adding whipping agent) that its weight is more original have dropped 30%.
Embodiment 5:
Hollow porous nanometer ZnO powder preparation method is see embodiment 1.
The SBS of the phosphite analog derivative of the antioxidant 1010 of 10 weight parts, 10 weight parts, 40 weight parts is mixed, makes modified additive. The whipping agent of the ABS masterbatch of 83 parts, 7 parts of modified additives, 5 parts of porous hollow nanometer ZnO powder, 3 parts of calcium carbonate and 2 parts is added after kneader heating mediates 1h, join in mixing roll. Being injected in the middle of tubular die by high-voltage high-speed in mixing roll, adopt low pressure foaming, be 7MPa in mold pressing, temperature is, at 60 DEG C, polymer melt is carried out foaming. Finally the cooling of shaping complete shell is deviate from from mould, after dry, obtain the aseptic tubing of foaming. After tubing is carried out cutting, the electronics cigarette shell that a kind of lightweight is antibacterial can be obtained. Prepare whipping agent addition 2%, nano-ZnO addition be 5% the sterilized electronic cigarette shell of lightweight, the tubing (not adding whipping agent) that its weight is more original have dropped 43%.
Embodiment 6:
Hollow porous nanometer ZnO powder preparation method is see embodiment 1.
By the TiO of the antioxidant 1010 of 10 weight parts, 15 weight parts2The SBS mixing of frothing aid and 30 weight parts, makes modified additive. The whipping agent of the PC master batches of 85 parts, 7 parts of modified additives, 3 parts of porous hollow nanometer ZnO powder, 3 parts of calcium carbonate and 2 parts is added after kneader heating mediates 4h, join in mixing roll. Being injected in the middle of tubular die by high-voltage high-speed in mixing roll, adopt low pressure foaming, be 6MPa in mold pressing, temperature is, at 70 DEG C, polymer melt is carried out foaming. Finally the cooling of shaping complete shell is deviate from from mould, after dry, obtain the aseptic tubing of foaming. After tubing is carried out cutting, the electronics cigarette shell that a kind of lightweight is antibacterial can be obtained. Prepare whipping agent addition 2%, nano-ZnO addition be 3% the sterilized electronic cigarette shell of lightweight, the tubing (not adding whipping agent) that its weight is more original have dropped 31%.
Embodiment 7:
Hollow porous nanometer ZnO powder preparation method is see embodiment 1.
By the TiO of the antioxidant 1010 of 10 weight parts, 15 weight parts2The SBS mixing of frothing aid and 30 weight parts, makes modified additive. The whipping agent of the PC master batches of 42 parts, the ABS masterbatch of 43 parts, 7 parts of modified additives, 3 parts of porous hollow nanometer ZnO powder, 3 parts of calcium carbonate and 2 parts is added after kneader heating mediates 3h, join in mixing roll.Being injected in the middle of tubular die by high-voltage high-speed in mixing roll, adopt low pressure foaming, be 5MPa in mold pressing, temperature is, at 40 DEG C, polymer melt is carried out foaming. Finally the cooling of shaping complete shell is deviate from from mould, after dry, obtain the aseptic tubing of foaming. After tubing is carried out cutting, the electronics cigarette shell that a kind of lightweight is antibacterial can be obtained. Prepare whipping agent addition 2%, nano-ZnO addition be 3% the sterilized electronic cigarette shell of lightweight, the tubing (not adding whipping agent) that its weight is more original have dropped 35%.
Embodiment 8:
As template taking the polyacrylic acid PAA (as 150nm, degree of crosslinking is 25% to particle diameter) that 0.5g is crosslinked, it is dispersed in the middle of 200mL deionized water, finally adds Zn (NO3)20.5g and urea 1.0g, and evenly stir and make it be dissolved completely in water. Whole system is transferred in the tetrafluoroethylene liner (volume is 300mL) of stainless steel autoclave, airtight good after transfer in the middle of baking oven, be heated to 200 DEG C and keep 12 hours. After reaction terminates, reactor is dropped to room temperature, by the mode of centrifugal (the centrifugal 2min of 12000rpm), the hollow porous ZnO obtained is separated, with deionized water wash 3 times, by vacuum drying method drying one day at 40 DEG C, both obtained hollow porous nanometer ZnO powder. The hollow porous ZnO nanoparticle of preparation is of a size of external diameter 560nm.
Mixing extrusion becomes the operational path of pipe see embodiment 2, obtains the electronics cigarette shell that lightweight is antibacterial.
Embodiment 9:
As template taking the polyacrylic acid PAA (as 150nm, degree of crosslinking is 25% to particle diameter) that 0.5g is crosslinked, it is dispersed in the middle of 200mL deionized water, finally adds ZnSO40.5g and urea 1.0g, and evenly stir and make it be dissolved completely in water. Whole system is transferred in the tetrafluoroethylene liner (volume is 300mL) of stainless steel autoclave, airtight good after transfer in the middle of baking oven, be heated to 120 DEG C and keep 36 hours. After reaction terminates, reactor is dropped to room temperature, by the mode of centrifugal (the centrifugal 7min of 5000rpm), the hollow porous ZnO obtained is separated, with deionized water wash 3 times, by vacuum drying method drying one day at 60 DEG C, both obtained hollow porous nanometer ZnO powder. The hollow porous ZnO nanoparticle of preparation is of a size of external diameter 490nm.
Mixing extrusion becomes the operational path of pipe see embodiment 2, obtains the electronics cigarette shell that lightweight is antibacterial.
Embodiment 10:
As template, it is dispersed in the middle of 200mL deionized water taking the polyacrylic acid PAA (as 150nm, degree of crosslinking is 25% to particle diameter) that 0.5g is crosslinked, finally adds zinc acetate 0.5g and urea 1.0g, and evenly stir and make it be dissolved completely in water. Whole system is transferred in the tetrafluoroethylene liner (volume is 300mL) of stainless steel autoclave, airtight good after transfer in the middle of baking oven, be heated to 200 DEG C and keep 24 hours. After reaction terminates, reactor is dropped to room temperature, by the mode of centrifugal (the centrifugal 7min of 6000rpm), the hollow porous ZnO obtained is separated, with deionized water wash 5 times, by vacuum drying method drying one day at 40 DEG C, both obtained hollow porous nanometer ZnO powder. The hollow porous ZnO nanoparticle of preparation is of a size of external diameter 510nm.
Mixing extrusion becomes the operational path of pipe see embodiment 2, obtains the electronics cigarette shell that lightweight is antibacterial.
Embodiment 11:
As template taking the polyacrylic acid PAA (as 150nm, degree of crosslinking is 25% to particle diameter) that 0.5g is crosslinked, it is dispersed in the middle of 200mL deionized water, finally adds ZnCl20.8g and urea 1.6g, and evenly stir and make it be dissolved completely in water.Whole system is transferred in the tetrafluoroethylene liner (volume is 300mL) of stainless steel autoclave, airtight good after transfer in the middle of baking oven, be heated to 120 DEG C and keep 24 hours. After reaction terminates, reactor is dropped to room temperature, by the mode of centrifugal (the centrifugal 7min of 8000rpm), the hollow porous ZnO obtained is separated, with deionized water wash 4 times, by vacuum drying method drying one day at 50 DEG C, both obtained hollow porous nanometer ZnO powder. The hollow porous ZnO nanoparticle of preparation is of a size of external diameter 800nm.
Mixing extrusion becomes the operational path of pipe see embodiment 2, obtains the electronics cigarette shell that lightweight is antibacterial.
Embodiment 12:
As template taking the polyacrylic acid PAA (as 150nm, degree of crosslinking is 25% to particle diameter) that 0.5g is crosslinked, it is dispersed in the middle of 200mL deionized water, finally adds ZnCl21.0g and urea 2.0g, and evenly stir and make it be dissolved completely in water. Whole system is transferred in the tetrafluoroethylene liner (volume is 300mL) of stainless steel autoclave, airtight good after transfer in the middle of baking oven, be heated to 160 DEG C and keep 20 hours. After reaction terminates, reactor is dropped to room temperature, by the mode of centrifugal (the centrifugal 7min of 8000rpm), the hollow porous ZnO obtained is separated, with deionized water wash 3 times, by vacuum drying method drying one day at 60 DEG C, both obtained hollow porous nanometer ZnO powder. The hollow porous ZnO nanoparticle of preparation is of a size of external diameter 1200nm.
Mixing extrusion becomes the operational path of pipe see embodiment 2, obtains the electronics cigarette shell that lightweight is antibacterial.
Embodiment 13:
As template taking the polyacrylic acid PAA (as 150nm, degree of crosslinking is 25% to particle diameter) that 0.5g is crosslinked, it is dispersed in the middle of 200mL deionized water, finally adds ZnCl20.5g and six methyne four ammonium 1.0g, and evenly stir and make it be dissolved completely in water. Whole system is transferred in the tetrafluoroethylene liner (volume is 300mL) of stainless steel autoclave, airtight good after transfer in the middle of baking oven, be heated to 200 DEG C and keep 12 hours. After reaction terminates, reactor is dropped to room temperature, by the mode of centrifugal (the centrifugal 7min of 8000rpm), the hollow porous ZnO obtained is separated, with deionized water wash 5 times, by vacuum drying method drying one day at 60 DEG C, both obtained hollow porous nanometer ZnO powder. The hollow porous ZnO nanoparticle of preparation is of a size of external diameter 630nm.
Mixing extrusion becomes the operational path of pipe see embodiment 2, obtains the electronics cigarette shell that lightweight is antibacterial.
Embodiment 14:
As template taking the polyacrylic acid PAA (as 150nm, degree of crosslinking is 25% to particle diameter) that 0.5g is crosslinked, it is dispersed in the middle of 200mL deionized water, finally adds ZnCl20.5g and thanomin 1.0g, and evenly stir and make it be dissolved completely in water. Whole system is transferred in the tetrafluoroethylene liner (volume is 300mL) of stainless steel autoclave, airtight good after transfer in the middle of baking oven, be heated to 200 DEG C and keep 36 hours. After reaction terminates, reactor is dropped to room temperature, by the mode of centrifugal (the centrifugal 7min of 8000rpm), the hollow porous ZnO obtained is separated, with deionized water wash 3～5 times, by vacuum drying method drying one day at 60 DEG C, both obtained hollow porous nanometer ZnO powder. The hollow porous ZnO nanoparticle of preparation is of a size of external diameter 480nm.
Mixing extrusion becomes the operational path of pipe see embodiment 2, obtains the electronics cigarette shell that lightweight is antibacterial.
Embodiment 15:
As template taking the polyacrylic acid PMAA (as 150nm, degree of crosslinking is 25% to particle diameter) that 0.5g is crosslinked, it is dispersed in the middle of 200mL deionized water, finally adds ZnCl20.5g and urea 1.0g, and evenly stir and make it be dissolved completely in water. Whole system is transferred in the tetrafluoroethylene liner (volume is 300mL) of stainless steel autoclave, airtight good after transfer in the middle of baking oven, be heated to 120 DEG C and keep 36 hours. After reaction terminates, reactor is dropped to room temperature, by the mode of centrifugal (the centrifugal 7min of 8000rpm), the hollow porous ZnO obtained is separated, with deionized water wash 5 times, by vacuum drying method drying one day at 60 DEG C, both obtained hollow porous nanometer ZnO powder. The hollow porous ZnO nanoparticle of preparation is of a size of external diameter 540nm.
Mixing extrusion becomes the operational path of pipe see embodiment 2, obtains the electronics cigarette shell that lightweight is antibacterial.

Claims (12)

1. the electronics cigarette shell that a lightweight is antibacterial, it is characterised in that, the relative density of the polymer pipe that aseptic foamable polymer tubing is more original reduces 10%～60%.
2. the electronics cigarette shell that a kind of lightweight as claimed in claim 1 is antibacterial, it is characterised in that, the preparation method of described electronics cigarette shell comprises the steps:
Step one, the crosslinked polyacrylic acid PAA of 0.1～5 weight part or crosslinked polymethyl acrylic acid PMAA is dispersed in the middle of the deionized water of 25～500 weight parts, adding the soluble zinc salt of 0.1～2.5 weight part and the aminated compounds of 0.4～8 weight part, stirring and dissolving, obtains reaction system; Reaction system is transferred in stainless steel autoclave, airtight good after transfer in baking oven, react 12～36 hours at 120～200 DEG C; Reactor being down to room temperature, under the rotating speed of 5000～12000rpm centrifugal 2～10 minutes, isolate hollow porous ZnO, with deionized water wash 3～5 times, at 40～60 DEG C, dry 24h, obtains hollow porous nanometer ZnO powder.
3. the electronics cigarette shell that a kind of lightweight as claimed in claim 2 is antibacterial, it is characterised in that, the preparation method of described electronics cigarette shell also comprises the steps:
Step 2, the whipping agent of the polymer masterbatch of 1～5 weight part porous hollow nanometer ZnO powder, 80～100 weight parts, 5～10 part by weight modified auxiliary agents, 1～3 weight parts of calcium carbonate and 1～4 weight part is added kneader heating kneading 1～5h, joining in mixing roll, high-voltage high-speed is injected into tubular die; It is 2～7MPa in mold pressing, when temperature is 50～80 DEG C, adopts low pressure foaming, polymer melt is carried out foaming; The cooling of shaping complete shell being deviate from from mould, cutting after dry, obtains the electronics cigarette shell that lightweight is antibacterial.
4. the electronics cigarette shell that lightweight according to claim 2 is antibacterial, it is characterised in that, in the preparation method of described electronics cigarette shell, described crosslinked PAA or crosslinked PMAA is prepared by distillation precipitation polymerization; The linking agent used is bi-vinyl bisacrylamide class linking agent, bi-vinyl di-esters linking agent or double-vinyl benzene class linking agent.
5. the electronics cigarette shell that lightweight according to claim 2 is antibacterial, it is characterized in that, in the preparation method of described electronics cigarette shell, the particle diameter of described crosslinked polyacrylic acid PAA or crosslinked polymethyl acrylic acid PMAA is 50～500nm, and degree of crosslinking is 10%～50%.
6. the electronics cigarette shell that lightweight according to claim 2 is antibacterial, it is characterised in that, in the preparation method of described electronics cigarette shell, in step one, soluble zinc salt is ZnCl2、Zn(NO3)2、ZnSO4Or zinc acetate.
7. the electronics cigarette shell that lightweight according to claim 2 is antibacterial, it is characterized in that, in the preparation method of described electronics cigarette shell, in step one, aminated compounds is selected from urea, six methyne four ammoniums, hydrazine hydrate, thanomin, diethanolamine and trimeric cyanamide.
8. the electronics cigarette shell that lightweight according to claim 3 is antibacterial, it is characterised in that, in the preparation method of described electronics cigarette shell, in step 2, polymer masterbatch is PC resin, ABS resin or both mixtures.
9. the electronics cigarette shell that lightweight according to claim 3 is antibacterial, it is characterized in that, in the preparation method of described electronics cigarette shell, modified additive described in step 2 is made up of the frothing aid of the antioxidant of 5～20 weight parts, 0～30 weight part and the toughner of 20～80 weight parts, and wherein toughner is one or several the mixture in SBS, SEBS and EVA; Frothing aid is TiO2Or TiO2With the mixture of ZnO; Antioxidant is quinoline derivatives, phosphite analog derivative.
10. the electronics cigarette shell that lightweight according to claim 3 is antibacterial, it is characterised in that: in described step 2, whipping agent is azo-compound, nitroso compound or the sodium carbonate salt master batch ball through polymer support Resin adhesive encapsulated.
11. according to the preparation method of the antibacterial electronics cigarette shell of described lightweight arbitrary in claim 1-10, it is characterised in that comprise the steps:
(1) using the crosslinked polyacrylic acid PAA of 0.1～5g or crosslinked polymethyl acrylic acid PMAA as template, it is dispersed in the middle of 25～500mL deionized water, finally add soluble zinc salt 0.1～2.5g and amine substance 0.4～8g, and evenly stir and make it be dissolved completely in water; The volume that whole system transfers to stainless steel autoclave is in the tetrafluoroethylene liner of 50～750mL, airtight good after transfer in the middle of baking oven, be heated to 120～200 DEG C and keep 12～36 hours; After reaction terminates, reactor is dropped to room temperature, by centrifugal mode, the hollow porous ZnO obtained is separated, with deionized water wash 3～5 times, by vacuum drying method drying one day at 40～60 DEG C, both obtained hollow porous nanometer ZnO powder;
(2), after the whipping agent of the polymer masterbatch of 80～100 parts, 5～10 parts of modified additives, 1～5 part of porous hollow nanometer ZnO powder, 1～3 part of calcium carbonate and 1～4 part being added kneader heating kneading 1～5h, join in mixing roll; Being injected in the middle of tubular die by high-voltage high-speed in mixing roll, adopt low pressure foaming, be 2～7MPa in mold pressing, temperature is, at 50～80 DEG C, polymer melt is carried out foaming; Finally the cooling of shaping complete shell is deviate from from mould, after dry, obtain the aseptic tubing of foaming. After tubing is carried out cutting, the electronics cigarette shell that a kind of lightweight is antibacterial can be obtained.
The preparation method of the electronics cigarette shell that 12. lightweights as claimed in claim 11 are antibacterial, it is characterised in that, in step (1):
The crosslinked PAA used replaces to crosslinked polymethyl acrylic acid PMAA; The linking agent used be selected from bi-vinyl bisacrylamide class, bi-vinyl di-esters and double-vinyl benzene class. The particle diameter of PAA or PMAA is 50～500nm, and degree of crosslinking is 10%～50%;
Soluble zinc salt is selected from ZnCl2、Zn(NO3)2、ZnSO4And zinc acetate;
Amine substance is selected from urea, six methyne four ammoniums, hydrazine hydrate, thanomin, diethanolamine and trimeric cyanamide;
The particle diameter of the hollow porous ZnO nanoparticle obtained is within the scope of 200～2000nm, and the size of hollow structure is within the scope of 50～400nm;
Centrifugal speed is 5000～12000rpm;
In step (2): polymer masterbatch be the one in PC resin and ABS resin or both admix use;
Modified additive is antioxidant, frothing aid and toughner, and wherein toughner is one or several the mixing in SBS, SEBS and EVA; Frothing aid is TiO2And ZnO and TiO2Mixture;
Whipping agent is the one in azo-compound, nitroso compound and sodium carbonate salt, through polymer support Resin adhesive encapsulated, it is the master batch ball of polymkeric substance.
CN201610043719.2A 2016-01-22 2016-01-22 A kind of electronic cigarette shell of lightweight antibacterial and preparation method thereof Active CN105670207B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108864674A (en) * 2017-05-11 2018-11-23 上海奥塞尔材料科技有限公司 Lighting polycarbonate compound and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101559974A (en) * 2009-05-14 2009-10-21 浙江理工大学 Method for preparing zinc oxide hollow microspheres
US20100278720A1 (en) * 2009-05-04 2010-11-04 Wong Stanislaus S Methods of Making Binary Metal Oxide Nanostructures and Methods of Controlling Morphology of Same
CN102082851A (en) * 2009-11-27 2011-06-01 常熟市广大电器有限公司 Antibacterial telephone set
CN102875955A (en) * 2012-10-08 2013-01-16 合肥杰事杰新材料股份有限公司 Plastic material with long-acting antibacterial effect and preparation method thereof
CN104804363A (en) * 2015-04-20 2015-07-29 青岛承天伟业机械制造有限公司 Plastic for toy for children
CN104853632A (en) * 2012-12-17 2015-08-19 Sis资源有限公司 Flavor enhancement for e-cigarette
CN105131554A (en) * 2015-09-18 2015-12-09 苏州新区佳合塑胶有限公司 Antibacterial composite material for mobile telephone shell

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100278720A1 (en) * 2009-05-04 2010-11-04 Wong Stanislaus S Methods of Making Binary Metal Oxide Nanostructures and Methods of Controlling Morphology of Same
CN101559974A (en) * 2009-05-14 2009-10-21 浙江理工大学 Method for preparing zinc oxide hollow microspheres
CN102082851A (en) * 2009-11-27 2011-06-01 常熟市广大电器有限公司 Antibacterial telephone set
CN102875955A (en) * 2012-10-08 2013-01-16 合肥杰事杰新材料股份有限公司 Plastic material with long-acting antibacterial effect and preparation method thereof
CN104853632A (en) * 2012-12-17 2015-08-19 Sis资源有限公司 Flavor enhancement for e-cigarette
CN104804363A (en) * 2015-04-20 2015-07-29 青岛承天伟业机械制造有限公司 Plastic for toy for children
CN105131554A (en) * 2015-09-18 2015-12-09 苏州新区佳合塑胶有限公司 Antibacterial composite material for mobile telephone shell

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108864674A (en) * 2017-05-11 2018-11-23 上海奥塞尔材料科技有限公司 Lighting polycarbonate compound and preparation method thereof

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